CN114807661B

CN114807661B - Porous iron-based amorphous/copper double-alloy composite material and preparation method and application thereof

Info

Publication number: CN114807661B
Application number: CN202210416193.3A
Authority: CN
Inventors: 曾德长; 韦靖; 郑志刚; 邱兆国; 黄磊
Original assignee: South China University of Technology SCUT
Current assignee: South China University of Technology SCUT
Priority date: 2022-04-20
Filing date: 2022-04-20
Publication date: 2023-09-26
Anticipated expiration: 2042-04-20
Also published as: CN114807661A

Abstract

The invention discloses a porous iron-based amorphous/copper double-alloy composite material and a preparation method and application thereof. The porous iron-based amorphous/copper double-alloy composite material is prepared by using a FeSiB amorphous alloy strip as a matrix material, putting the strip into chemical plating solution with a certain proportion, and plating a layer of copper on the surface of the strip by a chemical displacement plating method to obtain the porous iron-based amorphous/copper double-alloy composite strip. The treatment method greatly improves the degradation rate of the iron-based amorphous alloy in the process of degrading dye wastewater, and effectively widens the applicable pH range of the material. The chemical replacement copper plating method is simple and low in cost, so that the method for improving the iron-based amorphous has great potential in the aspect of dye wastewater treatment performance.

Description

Porous iron-based amorphous/copper double-alloy composite material and preparation method and application thereof

Technical Field

The invention relates to the field of Fe-based amorphous alloy materials, in particular to a porous iron-based amorphous/copper double-alloy composite material, and a preparation method and application thereof.

Background

Water is a living source, so how to effectively recycle water resources is a big problem in our country. With the rapid development of the economy in China, the limited fresh water resource is seriously polluted. The water pollution is mainly divided into industrial wastewater, domestic sewage and precipitation. Among them, the most serious hazard to the environment is industrial wastewater, which is due to the complex composition of the industrial wastewater and the huge two-discharge amount. Among various industrial waste water, the printing and dyeing waste water accounts for about 10% of the total discharge amount.

Dyes are classified according to chemical structure, and are mainly classified into azo dyes and other dyes. Azo dyes contain at least one azo group (-n=n-) and are linked to an aromatic structure. Because of the characteristics of low production cost, stable structure, difficult fading, rich color and the like, the dye is used in a large amount, and the dye accounts for about 60 to 70 percent of the total dye. Azo dye wastewater contains more organic matters, so that peripheral water bodies are anoxic and smelly; the deeper chromaticity can reduce the transmittance of the water body, thereby affecting the photosynthesis of plants and further preventing the healthy growth of the plants; carcinogens can be generated in the degradation process, and the health of human bodies is damaged. Therefore, the adoption of effective measures for treating azo dye wastewater is profoundly significant.

The current treatment method for azo dye wastewater mainly comprises the following steps: biological, physical and chemical methods each have advantages and disadvantages and therefore often require a combination of methods. For biological methods, the requirements on the environment are high and the degradation efficiency is low; while physical adsorption or separation processes merely transfer the contaminants and do not effect decomposition and mineralization of the azo dye; the chemical methods used, such as chemical oxidation, electrochemical, and zero-valent iron reduction, have the disadvantages of high power consumption, high operating cost, and much sludge.

In recent years, researchers have begun to use iron-based amorphous alloy materials to replace zero-valent iron powder for reductive degradation of azo dyes, with the degradation rate of iron-based amorphous alloys being 1000-fold higher than that of zero-valent iron powder (S.Xie, P.Huang, J.J.Kruzic, x. Zeng and h. Qian, A highly efficient degradation mechanism of methyl orange using Fe-based metallic glass powders.scientific reports,2016,6,1-10). Research is conducted on Fe ₇₈ Si ₁₁ B ₉ P ₂ Degradation performance of amorphous alloy to gold orange II azo dye compared with Fe ₇₈ Si ₁₃ B ₉ Amorphous alloy, degradation rate k _obs From 0.057min ^-1 Lifting to 0.082min ^-1 . However, the alloy had little degradation of the orange II azo dye at the initial pH=9 and pH=11 (Ji L, chen J W, zheng Z G, et al excelent degradation performance of the Fe) ₇₈ Si ₁₁ B ₉ P ₂ metallic glass in azo dye treatment[J]Journal of Physics and Chemistry of Solids,2020,145: 109546.). Therefore, the iron-based amorphous alloy has good application prospect in degrading printing and dyeing sewage (without illumination condition), but the application range of the degradation rate and pH is still expected to be further improved and widened.

Disclosure of Invention

The invention aims to provide a porous iron-based amorphous/copper double-alloy composite material, a preparation method thereof and application thereof in dye wastewater treatment.

The aim of the invention is achieved by the following technical scheme.

A porous Fe-based amorphous/copper double-alloy composite material is prepared from FeSiB amorphous alloy strip as matrix material and porous copper as surface coating. The FeSiB amorphous alloy strip has the composition of Fe _x Si _y B _z Wherein x, y and z respectively represent the atomic percentages of Fe, si and B in the alloy, x is more than or equal to 74 and less than or equal to 84,6, y is more than or equal to 16, z is more than or equal to 6 and less than or equal to 16, and x+y+z=100.

Preferably, the FeSiB amorphous alloy strip has a composition formula of Fe _77.5 Si _13.5 B ₉ The method comprises the steps of carrying out a first treatment on the surface of the The width was 10mm and the thickness was 22. Mu.m.

The preparation method of the porous iron-based amorphous/copper double-alloy composite material comprises the following steps:

(1) Weighing raw materials Fe, si and B according to the component content of the amorphous alloy strip, and smelting in an arc smelting furnace in an inert atmosphere to prepare an alloy;

(2) Preparing the alloy prepared in the step (1) into an amorphous alloy strip by adopting a single-roller melt-spinning method: after the raw materials in the step (1) are completely and uniformly melted, spraying melted metal liquid onto a roller through instantaneous pressure difference for melt-spinning to obtain an iron-based amorphous alloy strip;

(3) Uniformly mixing copper salt, complexing agent and water according to mass ratio to prepare chemical plating solution;

(4) Cutting the iron-based amorphous alloy strip obtained in the step (2) into blocks with the diameter of 10mm, throwing the blocks into the plating solution in the step (3) according to a certain weight, and carrying out chemical replacement copper plating;

(5) And (3) cleaning and drying the FeSiB/Cu double-alloy composite strip obtained in the step (4) to obtain the porous iron-based amorphous/copper double-alloy composite material.

Preferably, in the step (1), in order to ensure the compliance with the nominal composition, the raw materials are weighed by a high-precision electronic balance, and the purities of the raw materials Fe, si and B are all more than or equal to 99.9%.

Preferably, in the step (2), the rotating speed of the roller of the belt throwing device is preferably 40-60 m/s.

Preferably, the plating solution in the step (3) comprises the following components in percentage by mass:

copper salt 1-60 g/L

5-100 g/L complexing agent

The balance of water

Preferably, the copper salt in the step (3) is copper sulfate, copper chloride, copper sulfate hydrate or copper chloride hydrate; the complexing agent is one or the combination of two of disodium ethylenediamine tetraacetate and potassium sodium tartrate.

Preferably, the pH of the plating solution in the step (3) is 3-12.

Preferably, the weight-volume ratio of the iron-based amorphous alloy strip and the plating solution in the step (4) is 1-100 g/L.

Preferably, the conditions for electroless replacement copper plating in step (4) are: heating and stirring for 1-30 minutes in a water bath at 25-65 ℃ with stirring speed of 200-600 r/min.

The invention also provides application of the porous iron-based amorphous/copper double-alloy composite material in dye wastewater treatment.

The application is specifically as follows: and (3) putting the porous iron-based amorphous/copper double-alloy composite material into azo dye wastewater, and degrading azo dye. The concentration of the azo dye wastewater is 10-100 mg/L; the degradation temperature is 5-65 ℃; the pH value of the azo dye wastewater is 3-11; the degradation is carried out under the condition of stirring, and the stirring speed is 200-600 r/min.

Compared with the prior art, the invention has the following advantages:

(1) The FeSiB amorphous alloy strip is used as a copper plating matrix material, and the component has good amorphous forming capability, mature preparation process and low market price, and can be produced in a large scale.

(2) As a metastable state material, the porous iron-based amorphous/copper dual-alloy composite material has higher thermodynamic energy than the corresponding amorphous alloy, so that the activation energy required for chemical reaction is lower than that of the corresponding crystalline alloy, and the porous iron-based amorphous/copper dual-alloy composite material has higher reactivity than the FeSiB amorphous strip used at present.

(3) The chemical replacement copper plating process is simple and easy to operate, and the chemical plating solution does not contain formaldehyde and other harmful substances, so that the method is environment-friendly.

(4) According to the invention, the surface of the iron-based amorphous alloy strip is plated with a porous copper plating layer, and the porous structure of the surface layer and the nanoscale three-dimensional petal-shaped structure of a small amount of copper-iron oxides greatly increase the specific surface area of the surface of the strip, so that the adsorption effect of azo dye molecules is remarkably improved. In the process of catalytic degradation of azo dye, local primary cell effect is easier to generate due to the non-uniformity of components of the surface layer, thereby accelerating electron transfer, effectively improving the degradation rate of azo dye and the degradation rate k _obs Up to 0.217min ^-1 . Compared with other methods for improving the degradation rate of the azo dye by using other materials, the method is economical and practical, and has better application prospect and lower cost.

(5) The porous iron-based amorphous/copper double-alloy composite material prepared by the method still has excellent degradation performance under the weak alkaline condition, and has wider applicable environment compared with FeSiB amorphous strips and traditional iron-based amorphous materials.

Drawings

FIG. 1 is a porous Fe prepared in example 1 _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ XRD pattern of amorphous alloy ribbon;

FIG. 2 is a porous Fe prepared in example 1 _77.5 Si _13.5 B ₉ SEM images and partial magnified SEM images of the surface of the Cu dual alloy composite strip contacting the copper roll surface;

FIG. 3 is a porous Fe prepared in example 1 _77.5 Si _13.5 B ₉ Surface SEM image and partial magnified SEM image of the free surface of the Cu dual alloy composite strip;

FIG. 4 is a porous Fe prepared in example 1 _77.5 Si _13.5 B ₉ Cross-sectional SEM images of Cu dual alloy composite strip;

FIG. 5 is a porous Fe prepared in example 1 _77.5 Si _13.5 B ₉ Element distribution diagram of surface line scanning of Cu double alloy composite strip;

FIG. 6 is a porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ Absorbance graph of the solution after the amorphous alloy strip is treated with 40mg/L of gold orange II dye aqueous solution for different times;

FIG. 7 is a porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ C of amorphous alloy strip and pure copper powder to gold orange II azo dye _t /C ₀ Dynamically fitting a curve;

FIG. 8 is a porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ A comparison chart of the decoloring rate of the amorphous alloy strip and the pure copper powder to the gold orange II azo dye;

FIG. 9 is a porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ A comparison chart of the total organic carbon removal rate in the solution after the amorphous alloy strip material degrades the orange II azo dye for 60 minutes;

FIG. 10 is a porous Fe _77.5 Si _13.5 B ₉ The comparative graph of the decoloring rate of the Cu-double alloy composite strip on the orange II azo dye under different initial pH conditions.

Detailed Description

The following describes the embodiments of the present invention further with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.

Example 1

This example is made by way of illustration of porous Fe _77.5 Si _13.5 B ₉ Method for preparing Cu double alloy composite strip and comparing it with Fe _77.5 Si _13.5 B ₉ Amorphous alloy strip and pure copper powder to illustrate its decoloring effect and the effect of surface electroless copper plating on the degradation efficiency of amorphous alloy strip is illustrated in conjunction with the associated figures.

Fe _77.5 Si _13.5 B ₉ Preparation of Cu double alloy composite strip:

(1) Selecting Fe particles, si blocks and B particles which are commercially available and have high purity (the purity is more than 99.99%) as raw materials, firstly separating surface oxide skin of pure metal block Fe, putting the pure metal block Fe into absolute ethyl alcohol to prevent oxidation, and proportioning according to the atomic ratio of 77.5%, 13.5% and 9% of Fe, si and B respectively;

(2) Under the condition that high-purity (purity is more than 99.999%) argon is taken as a protective atmosphere, sponge titanium is taken as an oxygen absorbent, and the raw materials prepared in the step (1) are placed in a water-cooling crucible of a vacuum melting furnace to be repeatedly melted and turned over for 5 times, so that the uniformity of the cast ingot is ensured, and the ferroalloy cast ingot is obtained;

(3) Polishing the surface oxide skin of the ferroalloy cast ingot prepared in the step (2), then placing the ferroalloy cast ingot into a quartz test tube, uniformly melting the ferroalloy cast ingot by using an induction furnace under argon atmosphere, regulating the surface linear speed of a single-roller to be 50m/s, spraying molten metal liquid onto a copper-roller under the protection of inert gas for melt-spinning, and obtaining Fe with the width of about 10mm and the thickness of about 22 mu m _77.5 Si _13.5 B ₉ An amorphous alloy strip;

(4) Preparing electroless plating solution: 0.975g of CuSO ₄ ·5H ₂ O is dissolved by 99mL of deionized water, after being stirred uniformly, 1.45g of disodium edetate dihydrate is added continuously, and the mixture is placed in a water bath kettle at the temperature of 45 ℃ and stirred uniformly until the solution becomes clear.

(5) Accurately weigh 2.8g/L Fe _77.5 Si _13.5 B ₉ Cutting the alloy strip into square blocks with the length of about 10mm, throwing the square blocks into the step [ ]4) Placing the prepared electroless plating solution in a beaker filled with the plating solution in a water bath, wherein the set temperature of the water bath is 45 ℃, and the stirring speed is 350r/min by adding mechanical stirring.

(6) And (5) after 2 minutes, pouring the plating solution, adding deionized water, ultrasonically cleaning the strip for 3 times, and finally ultrasonically cleaning the strip with absolute ethyl alcohol for 1 time, wherein the cleaning time is 60 seconds each time, so that no impurity residue exists on the surface of the strip.

(7) Placing the strip obtained in the step (6) in a vacuum drying oven for vacuum drying, and drying to obtain porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip.

Porous Fe obtained in this example _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ The XRD test patterns of the strip are shown in FIG. 1. The porous Fe is shown in the figure _77.5 Si _13.5 B ₉ The Cu dual alloy composite strip exhibits three diffraction peaks at 2θ values of 43.3 °, 50.4 ° and 74.1 °, which correspond to the (111), (200) and (220) crystal planes of Cu, respectively. And Fe (Fe) _77.5 Si _13.5 B ₉ The strip exhibits a typical amorphous diffuse scattering peak, indicating that it is amorphous.

Porous Fe prepared in this example _77.5 Si _13.5 B ₉ The surface morphology of the Cu-dual alloy composite strip is shown in FIG. 2, wherein (a) in FIG. 2 is porous Fe _77.5 Si _13.5 B ₉ SEM image of the surface of the Cu dual alloy composite strip contacting the copper roll surface, and (b) in fig. 2 is a partial magnified SEM image thereof. The graph shows that the surface appearance of the obtained copper roller contact surface coating is complete, a small number of holes with diameters of about 5-10 mu m are formed, copper-iron oxides at the edges of the holes show a nanoscale three-dimensional petal-shaped structure, and the adsorption effect on dye molecules is enhanced by the existence of metal oxides; the interior of the hole exposes the iron-based amorphous matrix material, and the structure provides a galvanic corrosion path for subsequent degradation reaction, so that the electrode reaction and the electron transfer rate of iron are accelerated.

FIG. 3 shows porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite stripThe surface morphology of the free-surface coating, wherein (a) in FIG. 3 is porous Fe _77.5 Si _13.5 B ₉ Surface SEM image of free surface of Cu dual alloy composite strip, and (b) in fig. 3 is a partial magnified SEM image thereof. Compared with the plating layer of the contact surface of the copper roller, the number of holes on the surface of the plating layer of the free surface is greatly increased, the size is smaller and is 2-5 mu m, and the whole plating layer has a porous structure. In FIG. 3 (b), it can be seen that the inside of the porous structure is an iron-based amorphous matrix, and such porous structure increases the specific surface area of degradation reaction, thereby accelerating the adsorption process of azo dye and Fe ⁰ A reduction process for the same.

FIG. 4 is a porous Fe _77.5 Si _13.5 B ₉ The SEM image of the cross section of the Cu-double alloy composite strip shows that the junction of copper and iron-based amorphous is compact, and no obvious defect exists. FIG. 5 is a porous Fe _77.5 Si _13.5 B ₉ EDS line scanning spectrum of the Cu dual-alloy composite strip shows that copper plating layers are successfully prepared at two ends of the strip, the copper iron oxide content of the contact surface of the copper roller is high, and the thickness of the copper plating layers at the two ends is about 800nm.

Porous Fe obtained in this example _77.5 Si _13.5 B ₉ The application of the Cu-double alloy composite strip in the degradation treatment of sewage containing azo dyes comprises the following specific processes:

(1) Deionized water is used for preparing a gold orange II solution, and the concentration of gold orange II dye in the solution is 40mg/L for standby.

(2) 2.5g of porous Fe obtained in this example was weighed out _77.5 Si _13.5 B ₉ Cu double alloy composite strip, fe _77.5 Si _13.5 B ₉ The amorphous strip and the pure copper powder are respectively poured into 250mL of prepared gold orange II dye solution, the solution is stirred by using a mechanical stirrer at the temperature of 35 ℃ in a constant-temperature water bath, the rotating speed of the stirrer is 350r/min, about 5mL of the solution is extracted at regular intervals, and the spectrum measurement of an ultraviolet-visible light photometer is carried out. The time taken for the solution was 0 th, 5 th, 10 th, 20 th, 30 th and 60 th minutes, respectively.

After the time of the different degradation is over,the solution was almost colorless at about 20 minutes, and FIG. 6 is a porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ Graph of absorbance of the solution after various times of treatment of the amorphous alloy strip with 40mg/L of gold orange II dye aqueous solution. As seen from FIG. 6 (a), the characteristic peak at 484nm in the figure represents an azo double bond, porous Fe _77.5 Si _13.5 B ₉ The decrease rate of the peak intensity at 484nm of the Cu dual-alloy composite strip material in the first ten minutes of the reaction is obviously higher than that of Fe _77.5 Si _13.5 B ₉ Amorphous alloy ribbon (fig. 6 (b)), which demonstrates that the porous iron-based amorphous/copper dual alloy composite material possesses more excellent azo dye removal properties.

FIG. 7 is a porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ C of amorphous alloy strip and pure copper powder to gold orange II azo dye _t /C ₀ Kinetic fitting curve (k) _obs And R is ² ). According to Lanbert-beer law, peak intensity at 484nm representing azo double bond in gold orange II is converted into corresponding gold orange II concentration, and a fitted curve shows that the porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ The degradation reaction dynamics of two amorphous alloy strips meet a first-order reaction model, wherein k _obs Representing the degradation reaction rate. Porous Fe _77.5 Si _13.5 B ₉ The degradation rate of the Cu double alloy composite strip material to the orange II azo dye is compared with that of Fe _77.5 Si _13.5 B ₉ The amorphous alloy strip is improved by more than 92%. While single pure copper powder has little effect on degrading the orange II azo dye. This demonstrates that copper combined with the porous structure promotes the rate of degradation reaction of the iron-based amorphous alloy ribbon to azo dyes.

FIG. 8 is a porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip, fe _77.5 Si _13.5 B ₉ Comparison of decolorization ratio of amorphous alloy strip and pure copper powder to gold orange II azo dyeA drawing. The graph shows that the decoloring rate of pure copper powder to gold orange II azo dye is approximately equal to 0 percent, and the porous Fe _77.5 Si _13.5 B ₉ The decoloring rate of the orange II azo dye can reach 68% when the Cu double alloy strip reacts for 5 minutes, which is far higher than that of Fe _77.5 Si _13.5 B ₉ The decoloring rate of the amorphous alloy strip after 5 minutes reaction is 41.4 percent. Thus porous Fe _77.5 Si _13.5 B ₉ The Cu double alloy composite strip can meet the requirement of sewage treatment for quick decolorization.

FIG. 9 is a porous Fe _77.5 Si _13.5 B ₉ Cu double alloy composite strip and Fe _77.5 Si _13.5 B ₉ And (3) comparing the total organic carbon removal rate in the solution after the amorphous alloy strip material is degraded for 60 minutes with the gold orange II azo dye, wherein the organic carbon content in the solution can be used for reflecting the final mineralization result of the gold orange II azo dye. The porous Fe is shown in the figure _77.5 Si _13.5 B ₉ The total organic carbon removal rate in the solution after the Cu-double alloy composite strip is degraded for 60 minutes is up to 84.2 percent, which is far higher than that of Fe _77.5 Si _13.5 B ₉ 74.3% of amorphous alloy strip. This indicates porous Fe _77.5 Si _13.5 B ₉ The Cu-double alloy composite material can not only quickly adsorb dye molecules on the golden orange II azo dye, but also effectively mineralize the azo dye molecules into inorganic compounds.

FIG. 10 is a porous Fe _77.5 Si _13.5 B ₉ The comparative graph of the decoloring rate of the Cu-double alloy composite strip on the orange II azo dye under different initial pH conditions. The porous Fe is shown in the figure _77.5 Si _13.5 B ₉ The Cu bimetallic strip had decolorizing properties for gold orange ii over a wide pH range of ph=3 to 11. Particularly, the material shows excellent degradation capability under the weak alkaline condition, and the pH=9 is almost close to the decoloring performance under the neutral condition, which is the decoloring performance not possessed by other iron-based amorphous materials. The wider pH application range provides wider application prospect for the porous iron-based amorphous/copper double-alloy composite material.

Example 2

Fe _79.5 Si _11.5 B ₉ Cu double-bondPreparing a gold composite strip:

(1) Selecting Fe particles, si blocks and B particles which are commercially available and have high purity (the purity is more than 99.99%) as raw materials, firstly separating surface oxide skin of pure metal block Fe, putting the pure metal block Fe into absolute ethyl alcohol to prevent oxidation, and proportioning according to the atomic ratio of 79.5%, 11.5% and 9% of Fe, si and B respectively;

(3) Polishing the surface oxide skin of the ferroalloy cast ingot prepared in the step (2), then placing the ferroalloy cast ingot into a quartz test tube, uniformly melting the ferroalloy cast ingot in an argon atmosphere by using an induction furnace, regulating the surface linear speed of a single-roller to be 55m/s, spraying molten metal liquid onto a copper-roller under the protection of inert gas for melt-spinning, and obtaining Fe with the width of about 10mm and the thickness of about 22 mu m _79.5 Si _11.5 B ₉ An amorphous alloy strip;

(4) Preparing electroless plating solution: 1.95g of CuSO ₄ ·5H ₂ O is dissolved by 99mL of deionized water, after being stirred uniformly, 1.45g of disodium ethylene diamine tetraacetate dihydrate and 2.46g of potassium sodium tartrate are added continuously, and the mixture is placed in a water bath kettle at 35 ℃ and stirred uniformly until the solution becomes clear.

(5) Accurately weigh 2.8g/L Fe _79.5 Si _11.5 B ₉ Cutting the alloy strip into square blocks with the length of about 10mm, throwing the square blocks into the chemical plating solution prepared in the step (4), placing a beaker filled with the plating solution into a water bath, wherein the set temperature of the water bath is 35 ℃, and the stirring speed is 350r/min by adding mechanical stirring.

(6) And (5) after 4 minutes, pouring the plating solution, adding deionized water, ultrasonically cleaning the strip for 3 times, and finally ultrasonically cleaning the strip with absolute ethyl alcohol for 1 time, wherein the cleaning time is 60 seconds each time, so that no impurity residue exists on the surface of the strip.

(7) Placing the strip obtained in the step (6) in a vacuum drying oven for vacuum drying, and drying to obtain porous Fe _79.5 Si _11.5 B ₉ Cu double alloy composite strip.

Example 3

This example is made by way of illustration of porous Fe _77.5 Si _11.5 B ₁₁ A preparation method of a Cu double alloy composite strip.

Fe _77.5 Si _11.5 B ₁₁ Preparation of Cu double alloy composite strip:

(1) Selecting Fe particles, si blocks and B particles which are commercially available and have high purity (the purity is more than 99.99%) as raw materials, firstly separating surface oxide skin of pure metal block Fe, putting the pure metal block Fe into absolute ethyl alcohol to prevent oxidation, and proportioning according to the atomic ratio of 77.5%, 11.5% and 11% of Fe, si and B respectively;

(3) Polishing the surface oxide skin of the ferroalloy cast ingot prepared in the step (2), then placing the ferroalloy cast ingot into a quartz test tube, uniformly melting the ferroalloy cast ingot in an argon atmosphere by using an induction furnace, regulating the surface linear speed of a single-roller to be 45m/s, spraying molten metal liquid onto a copper-roller under the protection of inert gas for melt-spinning, and obtaining Fe with the width of about 10mm and the thickness of about 22 mu m _77.5 Si _11.5 B ₁₁ An amorphous alloy strip;

(4) Preparing electroless plating solution: 1.33g of CuCl ₂ ·2H ₂ O is dissolved by 99mL of deionized water, after being stirred uniformly, 1.45g of disodium edetate dihydrate is added continuously, and the mixture is placed in a water bath kettle at the temperature of 45 ℃ and stirred uniformly until the solution becomes clear.

(5) Accurately weigh 2.8g/L Fe _77.5 Si _11.5 B ₁₁ Cutting the alloy strip into square blocks with the length of about 10mm, throwing the square blocks into the chemical plating solution prepared in the step (4), placing a beaker filled with the plating solution into a water bath, wherein the set temperature of the water bath is 35 ℃, and the stirring speed is 350r/min by adding mechanical stirring.

(7) Placing the strip obtained in the step (6) in a vacuum drying oven for vacuum drying, and drying to obtain porous Fe _77.5 Si _11.5 B ₁₁ Cu double alloy composite strip.

The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims

1. The preparation method of the porous iron-based amorphous/copper double-alloy composite material is characterized in that a matrix material of the porous iron-based amorphous/copper double-alloy composite material is a FeSiB amorphous alloy strip, a surface coating is copper with a porous structure, the composition formula of the FeSiB amorphous alloy strip is FexSiyBz, wherein x, y and z respectively represent the atomic percentages of Fe, si and B in the alloy, x is more than or equal to 74 and less than or equal to 84,6, y is more than or equal to 16, z is more than or equal to 6 and less than or equal to 16, and x+y+z=100; the preparation method specifically comprises the following steps:

(4) Throwing the iron-based amorphous alloy strip obtained in the step (2) into the plating solution of the step (3) for chemical replacement copper plating;

(5) Cleaning and drying the FeSiB/Cu double-alloy composite strip obtained in the step (4) to obtain the porous iron-based amorphous/copper double-alloy composite material;

the copper salt in the step (3) is copper sulfate, copper chloride, copper sulfate hydrate or copper chloride hydrate; the complexing agent is one or the combination of two of disodium ethylenediamine tetraacetate and potassium sodium tartrate;

the mass concentration of the copper salt in the step (3) is 1-60 g/L, the mass concentration of the complexing agent is 5-100 g/L, and the pH value of the plating solution in the step (3) is 3-12;

the weight-volume ratio of the iron-based amorphous alloy strip to the plating solution in the step (4) is 1-100 g/L;

the conditions for electroless replacement copper plating in step (4) are: heating and stirring for 1-30 minutes in a water bath at 25-65 ℃ with stirring speed of 200-600 r/min.

2. The porous iron-based amorphous/copper dual-alloy composite material prepared by the preparation method of claim 1.

3. The use of a porous iron-based amorphous/copper dual alloy composite material according to claim 2 in dye wastewater treatment.

4. Use of a porous iron-based amorphous/copper double alloy composite material according to claim 3 in dye wastewater treatment, characterized in that the porous iron-based amorphous/copper double alloy composite material is put into azo dye wastewater, and azo dye is degraded.

5. The use of a porous iron-based amorphous/copper dual-alloy composite material in dye wastewater treatment according to claim 4, wherein the concentration of azo dye wastewater is 10-100 mg/L; the degradation temperature is 5-65 ℃; the pH value of the azo dye wastewater is 3-11; the degradation is carried out under the condition of stirring, and the stirring speed is 200-600 r/min.